CN109851778B - Method for preparing polybutyrolactam by anion ring-opening polymerization - Google Patents
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- 238000007151 ring opening polymerisation reaction Methods 0.000 title claims abstract description 12
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 25
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- 238000003756 stirring Methods 0.000 claims abstract description 22
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- 239000001569 carbon dioxide Substances 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 18
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 17
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims abstract description 17
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims abstract description 15
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
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- QEWFNTGJRKCBES-UHFFFAOYSA-N pyrrolidine;sodium Chemical compound [Na].C1CCNC1 QEWFNTGJRKCBES-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a method for preparing polybutyrolactam by anion ring-opening polymerization, which comprises the steps of activating potassium tert-butoxide, initiating by carbon dioxide, and adding paraffin oil and sodium dodecyl sulfate; the method starts from 2-pyrrolidone, and comprises the steps of activating potassium tert-butoxide, initiating by carbon dioxide, adding paraffin oil and sodium dodecyl sulfate for polymerization, adding n-hexane for stirring and suction filtration to finally obtain the polymer polybutyrolactam.
Description
Technical Field
The invention relates to a nylon synthesis process, in particular to a direct polymerization process of polybutyrolactam (nylon 4) by an anion ring opening mechanism.
Background
The polybutyrolactam 4 (PA 4, commonly called nylon 4) is polyamide with 4 carbon atoms in the structural unit, has the melting point of 260-270 ℃ due to the difference of atomic weight and structure, has the characteristics of good wear resistance, high corrosion resistance, strong fatigue resistance, outstanding dyeing performance and the like, has the highest hydrophilicity in nylon resin, is the only degradable nylon at present, and is mainly used for synthetic fibers, artificial leather, synthetic paper and the like. The artificial leather made of the polybutyrolactam has elasticity and porosity and does not generate static electricity; the plastic products processed by the injection molding and extrusion molding methods have excellent performance and wide application range. In addition, the polybutyrolactam has hydrophilicity similar to that of cotton and filament, and can be used as fiber drawing, filming agent or other forming compound. At present, most of traditional nylon materials such as PA, PA66 and the like are extracted from petroleum, not only pollute the environment, but also depend on scarce energy, and from the development point of view, the biomass nylon material must replace the traditional nylon material. The polymer polybutyrolactam is made from 2-pyrrolidone which can be transformed from aminobutyric acid by vegetable oil cracking method or biological fermentation method, and the biomass nylon has more environmental protection, low cost and high competitiveness. However, the polymerization of 2-pyrrolidone is a heterogeneous process with 'fast initiation and slow growth', and the problems of poor repeatability, small molecular weight and the like are not solved, so that the industrial production is not realized.
In 1982 John Wiley placed 200 g of 2-pyrrolidone and 15.5 g of potassium hydroxide in a 500ml flask, the mixture was heated for 20 minutes in a stream of nitrogen, distillation was started under a pressure of 5 mm Hg, and carbon dioxide gas was passed through the clear solution as it cooled to 30 ℃. 148 grams of the reaction mixture was then transferred to a polyethylene bottle and placed in an oven at 49-52 ℃ for 22 hours. The hardened polymer mass is decomposed into particles, washed with water until the pH value of the filtrate is 6.5, and then dried in the environment at 70 ℃ in vacuum to prepare the nylon 4. 5g of polymer are dissolved in 100ml of 90% formic acid at room temperature. The viscous solution was added dropwise to 2 liters of water to form a precipitate. The filtered precipitate was washed with clean water until the ph of the filtrate reached 7, and dried in a vacuum oven at 70 ℃. The reprecipitated polymer was washed twice with the above 90% formic acid-water method, and the specific viscosity of the polymer was substantially unchanged.
Bacska in 1985i denotes py and CH3ONa is used as a raw material to prepare the pyrrolidine sodium. Methanol formed in the reaction process is removed by azeotropic distillation. The py-Na or sodium pyrrolidonecarboxylate (py-Na/CO) obtained by reaction with carbon dioxide is filtered off in suspension as a white solid2). In a dry polyethylene bottle, polymerization is carried out by mixing py with a predetermined amount of a catalyst, an initiator or other additives and heating under an atmosphere of nitrogen gas, and hardened into a block-like polymer, which is in a microscopic form into a granular form, washed with distilled water and dried in a vacuum oven. The main purpose is to study the influence of the concentration of initiator, catalyst and the like on the conversion rate of nylon 4.
Both of the above documents are bulk polymerizations. The polymerized polymers are all hardened blocks. The method can be carried out in a laboratory, but is not beneficial to subsequent processing in industrial production, is easy to block pipelines, is difficult to discharge, and the particles are in a microscopic state and are not directly polymerized into small balls.
A method for preparing nylon 4 microspheres by a heterogeneous polymerization method was described in 2015 by Nam chell Kim et al. The polymerization reaction of 2-pyrrolidone (C4) is mainly carried out by taking paraffin oil/C4 as an inhomogeneous medium and sodium dodecyl sulfate, potassium tert-butoxide and benzoyl chloride as raw materials. The influence of polymerization variables such as stirring speed, phase ratio, emulsifier and catalyst concentration on the polymerization was examined from the viewpoints of polymerization yield, particle size and particle size distribution. By adjusting the experimental conditions, the non-solidified nylon 4 microspheres with the average particle size of 9.6-110.9 mm and the yield of 76% can be prepared. When benzoyl chloride is used as an initiator, the polymerization speed is high, and the benzoyl chloride is used as the initiator, so that the benzoyl chloride is toxic and is not suitable for industrial application; the second benzoyl chloride initiated polymerization, the polymer molecular weight is small and the thermal stability is also poor.
In the prior art, the polymerization of 2-pyrrolidone is adopted to prepare the polybutyrolactam, which has the following technical problems:
(1) the reaction speed of the common anion ring-opening polymerization method is too fast and difficult to control, and the polymer is condensed into hard blocks in a reaction kettle, blocks pipelines and is difficult to discharge, so that the method cannot be applied to large-scale production.
(2) The yield is low.
(3) If the polymerization is stopped by adding a large amount of hot water in the middle of the polymerization reaction for the purpose of facilitating the discharge, the problem of difficult discharge is solved, but the molecular weight of the polymer obtained by the method is very small, and the application requirement cannot be met.
The molecular weight of the polybutyrolactam prepared by the prior art is about thousands to 10000.
(4) The thermal stability is poor.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a method for preparing polybutyrolactam by anion ring-opening polymerization, which directly starts from 2-pyrrolidone, takes half of the activation liquid after the activation of potassium tert-butoxide, leads in carbon dioxide for initiation, adds paraffin oil and sodium dodecyl sulfate, then adds the other half of the activation liquid again, and finally adds normal hexane, finally obtains the polybutyrolactam.
The invention aims to:
(1) the prepared polybutyrolactam has large molecular weight;
(2) the polymerization speed is convenient to control, the polymer is not coagulated in the reaction kettle, and the discharging is simple and easy;
(4) high yield, good thermal stability and low cost.
In order to realize the purpose, the invention adopts the following technical scheme:
a method for preparing polybutyrolactam by anion ring-opening polymerization comprises activating potassium tert-butoxide, initiating by carbon dioxide, and adding paraffin oil and sodium dodecyl sulfate.
The method specifically comprises the following steps:
(1) potassium tert-butoxide activation
6-15 parts by mass of 2-pyrrolidone is put into a reaction kettle which is pre-dried, deaerated and filled with nitrogen. Closing the nitrogen, starting the vacuum state, heating and stirring to 60-100 ℃, keeping the temperature for 0.5-8 hours, and controlling the rotating speed at 400 r/min. And (3) closing the vacuum device, introducing nitrogen, continuously adding 0.5-6 parts (by mass) of potassium tert-butoxide into the reaction kettle, closing the nitrogen after adding, continuously vacuumizing, and preserving heat at 60-100 ℃ for 2-6 hours to prepare the activating solution.
(2) Initiation by carbon dioxide
And closing the vacuum device of the activating solution, taking out half of the solution in the reaction kettle, pouring the half of the solution into another flask, heating to 15-50 ℃, introducing carbon dioxide for 5-30 minutes, wherein the flow rate is 2-3L/min, and the stirring speed is 180 r/min.
(3) Adding paraffin oil and sodium dodecyl sulfate
And then sequentially adding 30-50 parts by mass of paraffin oil, 1 part by mass of sodium dodecyl sulfate and the rest half solution in the reaction kettle, heating to 70-120 ℃ under a vacuum condition, keeping the temperature for 1-6 hours, heating to 30-70 ℃, stirring at the rotation speed of 300-400r/min, and continuing to carry out closed reaction for 18-72 hours.
(4) Adding n-hexane
Adding 20-45 parts (by mass) of n-hexane, stirring for 3-48 hours, and performing suction filtration to obtain the polymer. And washing the polymer with acetone, washing with water, and drying in a vacuum oven to obtain a white solid, namely the polymer polybutyrolactam.
The preferable technical scheme is as follows:
(1) potassium tert-butoxide activation
6-9 parts by mass of 2-pyrrolidone is put into a reaction kettle which is pre-dried, deaerated and filled with nitrogen. Closing the nitrogen, starting the vacuum state, heating and stirring to 80-90 ℃, preserving the heat for 1.5-3.5 hours, and controlling the rotating speed at 400 r/min. And (3) closing the vacuum device, introducing nitrogen, continuously adding 1-1.5 parts (by mass) of potassium tert-butoxide into the reaction kettle, closing the nitrogen after adding, continuously vacuumizing, and preserving heat at 80-90 ℃ for 2-3 hours to prepare the activation liquid.
(2) Initiation by carbon dioxide
And closing the vacuum device of the activating solution, taking out half of the solution in the reaction kettle, pouring the half of the solution into another flask, heating to 40-50 ℃, introducing carbon dioxide for 10-15 minutes, wherein the flow rate is 2-3L/min, and the stirring speed is 180 r/min.
(3) Adding paraffin oil and sodium dodecyl sulfate
And then sequentially adding 40-50 parts by mass of paraffin oil, 1 part by mass of sodium dodecyl sulfate and the rest half solution in the reaction kettle, heating to 80-90 ℃ under a vacuum condition, keeping the temperature for 2-3 hours, heating to 40-50 ℃, stirring at the rotation speed of 300-400r/min, and continuing to carry out closed reaction for 36-72 hours.
(4) Adding n-hexane
Adding 25-35 parts (by mass) of n-hexane, stirring for 6-8 hours, and performing suction filtration to obtain the polymer. And washing the polymer with acetone, washing with water, and drying in a vacuum oven to obtain a white solid, namely the polymer polybutyrolactam.
By adopting the technical scheme, the invention has the beneficial effects that:
(1) the molecular weight of the nylon 4 prepared by the invention is more than 20000-40000; good stability, and the maximum thermal decomposition rate temperature is about 270 ℃.
(2) The reaction speed is slow and controllable, and in the reaction process, the polymer is dissolved in the solvent, so that the polymerization reaction is slowly and uniformly carried out in the solvent, and the defect of difficult discharging of bulk polymerization is fundamentally solved;
in the prior art, the reaction speed is high, the agglomeration is easy, the mass polymerization can be coagulated into hard blocks within several hours, the reaction speed is slow, and the polymerization lasts for 3 days and is still liquid.
(3) The yield of the polybutyrolactam prepared by the invention is 79-83%.
(4) Compared with the prior nylon 4 synthesis technology, the invention has low price and can reduce the cost by about 30 percent; the raw and other materials low price that this patent used, paraffin oil, n-hexane all can retrieve, handle the back and recycle in the later stage moreover.
Drawings
FIG. 1 is a schematic view of the polymerization process of the present invention.
Detailed Description
In order to make the technical means, innovative features and operating steps provided by the present invention easy to understand, the present invention is further explained below with reference to specific embodiments.
The present invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting to the scope of the invention.
Example 1
This example provides a ring-opening polymerization method for synthesizing polybutyrolactam, which includes the following steps:
(1) potassium tert-butoxide activation
Adding 30g of 2-pyrrolidone into a 250ml three-neck flask filled with nitrogen, stirring at the speed of 150r/min, closing the nitrogen, vacuumizing, heating to 80 ℃, and preserving heat for 3 hours; and (3) closing the vacuum, introducing nitrogen, adding 5g of potassium tert-butoxide under the protection of the nitrogen, closing the nitrogen again, vacuumizing, and preserving the heat at 80 ℃ for 2 hours to obtain the activating solution.
(2) Initiation by carbon dioxide
And (3) introducing nitrogen into another 500ml three-neck flask, adding half of the activating solution, sealing the nitrogen, heating to 40 ℃, introducing dry carbon dioxide gas, setting the flow rate to be 2.5L/min, introducing for 15 min, and stirring at the speed of 180 r/min.
(3) Adding paraffin oil and sodium dodecyl sulfate
And starting nitrogen again, sequentially adding 180g of paraffin oil which is vacuumized and heated to 90 ℃ in advance, preserving heat for 2h, setting the stirring speed to be 180r/min, 4g of sodium dodecyl sulfate and the other half of activating solution, heating to 50 ℃, setting the stirring speed to be 400r/min, and reacting for 36 h.
(4) Adding n-hexane
Adding 120g of normal hexane, stirring for more than 8h, carrying out suction filtration to obtain a product, washing with acetone for three times, then washing with water for three times, and placing in a vacuum oven at 60 ℃ for drying for 24h to finally obtain a milky white solid, namely polybutyrolactam nylon 4, wherein the product yield is 79 percent and the molecular weight is more than 20000.
Example 2
This example continues to provide a method for synthesizing polybutyrolactam by anion ring-opening polymerization, comprising the steps of:
(1) potassium tert-butoxide activation
30g of 2-pyrrolidone were charged into a 250ml three-necked flask filled with nitrogen. Stirring at 150r/min, turning off nitrogen, vacuumizing, heating to 90 deg.C, and maintaining for 2 hr. After the vacuum was turned off, nitrogen was purged and 5g of potassium tert-butoxide was added under nitrogen protection. And closing the nitrogen again, vacuumizing, and preserving the heat at 90 ℃ for 3 hours to obtain the activation solution.
(2) Initiation by carbon dioxide
And (3) taking another 500ml three-neck flask, introducing nitrogen, adding half of the activating solution, sealing the nitrogen, heating to 50 ℃, introducing dry carbon dioxide gas, setting the flow rate to be 3L/min, introducing the carbon dioxide for 10 min, and stirring at the speed of 180 r/min.
(3) Adding paraffin oil and sodium dodecyl sulfate
And starting nitrogen again, sequentially adding 180g of paraffin oil which is vacuumized and heated to 85 ℃ in advance, preserving heat for 3h, setting the stirring speed to be 180r/min, 4g of sodium dodecyl sulfate and the other half of activating solution, heating to 45 ℃, setting the stirring speed to be 300r/min, and reacting for 72 h.
(4) Adding n-hexane
Adding 120g of normal hexane, stirring for more than 6h, carrying out suction filtration to obtain a product, washing with acetone for three times, then washing with water for three times, and placing in a vacuum oven at 70 ℃ for drying for 24h to finally obtain a milky white solid, wherein the yield of the polybutyrolactam nylon 4 product is 83%. The molecular weight of the prepared polybutyrolactam reaches about 26000.
Claims (4)
1. A method for preparing polybutyrolactam by anion ring-opening polymerization is characterized in that: the method comprises activating potassium tert-butoxide, initiating with carbon dioxide, adding paraffin oil and sodium dodecyl sulfate, and adding n-hexane; the mass parts of the reaction raw materials are as follows: 6-9 parts of 2-pyrrolidone, 1-1.5 parts of potassium tert-butoxide, 40-50 parts of paraffin oil and 1 part of sodium dodecyl sulfate;
activating the potassium tert-butoxide, namely putting 2-pyrrolidone into a reaction kettle under the protection of nitrogen, heating and stirring to 60-100 ℃ in a vacuum state, preserving heat for 0.5-8 hours, closing a vacuum device, adding the potassium tert-butoxide under the protection of nitrogen, closing the nitrogen after adding, continuing vacuumizing, and preserving heat for 2-6 hours at 60-100 ℃ to prepare an activating solution;
initiating by using carbon dioxide, taking half of the active liquid in the reaction kettle, heating to 15-50 ℃, and introducing carbon dioxide for 5-30 minutes at a flow rate of 2-3L/min;
adding paraffin oil and sodium dodecyl sulfate, sequentially adding paraffin oil, sodium dodecyl sulfate and the rest half of the activation solution in the reaction kettle, heating to 30-70 ℃, and continuing to perform closed reaction for 18-72 hours; the normal hexane is added, and the mass ratio of the normal hexane to the 2-pyrrolidone is as follows: 20-45:6-15.
2. The method for preparing polybutyrolactam by anion ring-opening polymerization according to claim 1, wherein: the paraffin oil is heated to 70-120 ℃ in advance under the condition of vacuum pumping, and the temperature is kept for 1-6 hours.
3. The method for preparing polybutyrolactam by anion ring-opening polymerization according to claim 1, wherein: adding n-hexane, stirring for 3-48 hours, carrying out suction filtration to obtain a polymer, washing the polymer with acetone, washing with water, and drying to obtain a white solid, namely the polymer polybutyrolactam.
4. The method for preparing polybutyrolactam by anion ring-opening polymerization according to claim 1, wherein: the molecular weight of the polybutyrolactam is more than 20000-40000, and the yield is 79-83%; the maximum thermal decomposition rate temperature was 270 ℃.
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| CN108047443A (en) * | 2017-12-25 | 2018-05-18 | 恒天生物基材料工程技术（宁波）有限公司 | A kind of synthesis technology of the polybutyrolactam based on anionic ring-opening polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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